Antioxidant salt



Patented June 13, 1950 ANTIOXIDANT SALT Lloyd A. Hall, Chicago, and Louis Sair, Evergreen Park, Ill., assignors to The Griiiith Laboratories, Inc., a corporation of Illinois No Drawing. Application May 18, 1048, Serial No. 27,837

17 Claims.

This invention relates to a non-toxic antioxidant salt for use on food materials containing oils or fats and requiring salt, such as potato chips and nuts, and relates particularly to ordinary table salt having associated therewith an antioxidant acid, particularly of the class consisting of benzoic, fumaric, tartaric, phosphoric, ascorbic and citric acids, or combinations thereof, in combination with a gallic ester and a nontoxic polyhydric alcohol.

The antioxidant salt of this invention is particularly adaptable for use in and on foods containing edible fats. It is particularly applicable for use on foods that are cooked in fats at relatively high temperatures as the salt may be added after the cooking operation has been completed. In the past, it has been customary to add an antioxidant to the oil or fat prior to the cooking with the intention that the fat remaining in the food after the cooking operation contain some or the antioxidant and thus be stabilized. It has been found, however, that the high temperatures used in the cooking operation destroys or materially reduces the eilect or the antioxidant material. As almost all foods that are cooked in heated fat are afterwards salted, it has been discovered that the antioxidant can be carried by the salt and thus dispersed on and through the cooked food. The antioxidant which is carried by the salt is then transferred to the oil and stabilizes the oil. The foods which are particularly applicable for treatment with the new antioxidant salt include potato chips and nuts as these two foods are ordinarily cooked in fat at high temperatures and salted rather heavily after they have been when.

In preparing the antioxidant composition of this invention, a non-toxic polyhydric alcohol such as propylene glycol 01' glycerine is used as a carrier for the gallic ester and the antioxidant acid. Both the ester and the acid are readily soluble in the alcohol and the resulting antioxidant composition readily adheres to the particles of salt and is thus easily dispersed on and through the fat when the salt is applied to or sprinkled on the food. All constituents of the antioxidant salt are anhydrous. The salt serves as a carrier for the antioxidant composition.

The gallic esters that may be used are preferably the methyl gallate, ethyl gallate, propyl gallate, butyl gallate, hexyl gallate, lauryl gallate and mixtures thereoi.

2 In preparing the antioxidant, it is preferred that the following proportions be used:

Table I Per cent Gallic ester 15 to 35 Antioxidant acid 15 to 85 Non-toxic polyhydric alcohol to 30 All ingredients should be substantially anhydrous. In a preferred method of making the antioxidant, the polyhydric alcohol is warmed and the antioxidant acid is added thereto. The mixture is agitated until all the acid has been dissolved. Then one-half of the gallic ester is added and agitation is continued until this portion has been dissolved. Following this, the other half of the ester is added and the mixture agitated until the ester has been dissolved. The antioxidant composition is then added to dry, fine salt in the proportions of between about 5 and 1% by weight of the salt. The salt and the antioxidant are agitated in an ordinary mixer until the antioxidant has been uniformly distributed over the salt. It is necessary that the final product be dry to the touch and be free flowing. The antioxidant salt will then preferably have the following proportions:

Table II Per cent Gallic ester 0.015 to 0.35 Antioxidant acid 0.015 to 0.35 Polyhydric alcohol 0.070 to 0.30

Salt 99.900 to 99.00

Table III Per cent Propyl gallate 28.1 Citric acid 26.1 Propylene glycol 45.8

Table IV Per cent Propyl gallate 0.101 Citric acid 0.004 Propylene glycol 0.105 Bait 09.040

Alter the antioxidant salt has been prepared. it can be exposed to air at room temperature for a relatively great length 01' time without any appreciable reduction in the activity of the salt. It is preferred, however, that it not be exposed to air for more than approximately one month.

Any amounts of the salt desired may be used on the foods. In preparing potato chips, for example, approximately 3-5% by weight of salt is ordinarily added to the chips. The cooked chips themselves ordinarily contain about 40% oil by weight. Thus 100 pounds of prepared potato chips will contain approximately 40 pounds 01. the oil.

In another embodiment of the invention an antioxidant composition was prepared containing 24.8 pounds (24.1%) 01' propyl gallate, 25.5 pounds (24.7%) of anhydrous citric acid, and 52.7 pounds (51.2%) of propylene glycol. This antioxidant was prepared by the method set forth hereinabove. It was found that the addition of 0.405 pounds (0.4%) of this antioxidant to 100 pounds (99.6%) of dry salt produced a free-flowing salt product having the following proportions:

Table V Per cent Propyl ga1late 0.096 Citric acid 0.099 Propylene glycol 0.200 Salt 09.800

Wing results were obtained:

Table VI Peroxide Value of 14rd Days oifitorage at 140 1.

Belt with no Antioxidant Antioxidant Belt The above tests show that within three days the lard in the potato chips on which no antioxidant was used was ver rancid with the lard having a peroxide value of 150. Alter five days the lard on the chips containing the antioxidant salt had a peroxide value of only 07.

Potato chips were also tried in corn oil at a temperature of 350-875" F. The procedure tollowed was the same as that given above with respect to the lard. The eil'ect of the antioxidant salt in retarding rancidity in the oil in the potato chips is shown in the following table:

Table VI! of Peroxide Value 0! Corn oil as 1 Salt with an antioxidant Antioxidant an (L 0. n 0. 4.0. 4.0. 12.2.. 6.5. 10 10.0 (odor htly oil)---" 10.8. 1 it {smells q to rancid).. 10. 1 70 very ranoid)- 30 good). 7 1B0. 80 very slightly oil).

U] rancid).

These tests show that the oil was rancid in the potato chips on which no antioxidant was used while those on which the antioxidant salt was used were only very slightly oil in odor and taste after 17 days and did not become rancid until 21 days.

Tests were conducted with the new antioxidant salt on cooked nuts. In one test 10 pounds or red-coat peanuts were cooked in hydrogenated cottonseed oil at 400-480 F. At the end oi the cooking, 1.5 ounces of butter were added to the cooked nuts and then 3 ounces or the new antioxidant salt were mixed in with one-hall or the nuts and the same amount of regular salt was mixed in with the other hall of the nuts. Both portions were incubated at F. The peroxide values of both portions oi nuts were determined at intervals. The peroxide values, determining rancidity development, were recorded as m1. of 0.002 N thiosuliate required for 1 gm. of unground nuts. The following results were obtained:

Table VIII 0 M1. or 'lhlosullats per gm. of nuts Storage at Belt with no Antioxidant Antioxidant em 2 0.55 ml. 0 net I. ood ii 0.80 ml. gra ncidLnflnn 1 3 (g 4 1.2 ml. (very rancid)" Do. is Do. 17 Do. as 0.05 ml. (little oil).

Similar tests were conducted by using pecans as the nuts. The following results were obtained:

Table IX S M1. oi'lhiosuli'sts per gm. slant:

Bolt wltli no Antioxidant Antioxidant Salt 28 Do. Iii Do.

Similar tests were conducted on cashew nuts and the following results were obtained:

Table X Days of M1. or 'lhiosuifate per gm. of nuts Storage at 140 Salt with no Antioxidant Antioxidant Salt Good 0d. 0.1 ml. (slightly ofi). zero mi. (good). zero ml. (good) Do. Lero nil. (good) Do. 0.3 ml. (slightly oil) ilo. 0.4 ml. of!) Do. 0.4 ml. ofl) l. trace oil.

In general, the preferred gallates are propyl, lauryl, and hexyl galiates while the preferred antioxidant 'acids are citric, ascorbic and phosphoric acids.

The foregoing detailed description is given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, for some modifications will be obvious to those skilled in the art.

We claim:

1. An antioxidant composition comprising about 0.015 to 0.35% by weight of an antioxidant acid of the class consisting of benzoic, fumaric. tartaric, phosphoric, ascorbic and citric acids, about 0.015 to 0.35% of a gallic ester of the class consisting of methyl, ethyl, propyl, butyl, hexyl and lauryl gallates, and about 0.070 to 0.30% of a non-toxic polyhydric alcohol associated with a carrier for the antioxidant comprising table salt, said proportions being by weight of the composition including the table salt.

2. The antioxidant composition of claim 1 wherein the alcohol comprises propylene glycol.

3. The antioxidant of claim 1 wherein the alcohol comprises glycerine.

4. The antioxidant composition of claim 1 wherein the antioxidant acid comprises citric acid.

5. The antioxidant composition of claim 1 whgrein the antioxidant acid comppises ascorbic aci 6. The antioxidant composition 01 claim 1 wherein the antioxidant acid comprises phosphoric acid.

7. The antioxidant composition of claim 1 wherein the ester comprises propyl gallate.

8. The antioxidant composition of claim 1 wherein the ester comprises lauryl gallate.

9. The antioxidant composition of claim 1 wherein the ester comprises hexyl gallate.

10. An antioxidant composition comprising from 0.015 to 0.35% by weight of an antioxidant acid 01' the class consisting of benzoic, fumaric, tartaric, phosphoric, ascorbic, and citric acids, from 0.015 to 0.35% of a gallic ester of the class consisting of methyl, ethyl, propyl, butyl, hexyl and lauryl gallates, and from 0.070 to 0.30% of propylene glycol associated with 99.9 to 99.0% of table salt as a carrier.

11. A fatty food in combination with an antioxidant comprising about 0.015 to 0.35% by weight of an antioxidant acid of the class consisting of benzoic, tumaric, tartaric, phosphoric. ascorbic and citric acids, about 0.015 to 0.35% of a gallic ester of the class consisting of methyl, ethyl, propyl, butyl, hexyl and lauryl gallates, about 0.070 to 0.30% of a non-toxic polyhydric alcohol, and a carrier for the antioxidant comprising table salt, said proportions being by weight of the composition including the table salt.

12. The combination of claim 11 wherein the fatty food comprises cooked nuts.

13. The combination of claim 11 wherein the fatty food comprises cooked potato chips.

14. A fatty food in combination with an antioxidant comprising from 0.015 to 0.35% by weight of an antioxidant acid of the clttss consisting of benzoic, fumaric, tartaric, phosphoric, ascorbic and citric acids, from 0.015 to 0.35% of a gallic ester of the class consisting of methyl, ethyl, propyl, butyl, and lauryl gallates, from 0.070 to 0.30% of propylene glycol and 99.9 to 99.0% of table salt as a carrier.

15. The combination of claim 14 wherein the fatty food comprises cooked potato chips.

16. The combination of claim 14 wherein the fatty food comprises cooked nuts.

17. A substantially dry tree-flowing table salt having distributed therethrough and carried thereby an anti-oxidant composition comprising as the active antioxidant ingredients approximately equal proportions of an ester of the class consisting of methyl, ethyl, propyl, butyl, hexyl and lauryl gallates and an acid of the class consisting of benzoic, fumaric, tartaric, phosphoric. ascorbic and citric acids, together with a nontoxic polyhydric alcohol in an amount approximately double the amount of said ester.

LLOYD A. HALL. LOUIS SAIR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,831,728 Working Nov. 10, 1931 2,029,248 Musher Jan. 28, 1936 2,334,401 Fitzpatrick Nov. 16, 1943 2,444,307 Penn June 29, 1948 OTHER REFERENCES Bergel, Chem. 8: Ind., Apr. 1944, pa es 127-128. Riemenschneider, Trans. Am. Assoc. Cereal Chem, p. 57, Apr. 1947. 

1. AN ANTIOXIDANT COMPOSITION COMPRISING ABOUT 0.015 TO 0.35% BY WIGHT OF AN ANTIOXIDANT ACID OF THE CLASS CONSISTING OF BENZOIC, FUMARIC, TARTARIC, PHOSPHORIC, ASCORBIC AND CITRIC ACIDS, ABOUT 0.015 TO 0.35% OF A GALLIC ESTER OF THE CLASS CONSISTING OF METHYL, ETHYL, PROPYL, BUTYL, HEXYL AND LAURYL GALLATES, AND ABOUT 0.070 TO 0.30% OF A NON-TOXIC POLYHYDRIC ALCOHOL ASSOCIATED WITH A CARRIER FOR THE ANTIOXIDANT COMPRISING TABLE SALT, SAID PROPORTIONS BEING BY WEIGHT OF THE COMPOSITION INCLUDING THE TABLE SALT. 